Process of chlorinating organic bodies.



O. ELLIS & K. P. MGBLROY.

PROCESS OF GHLORINATING ORGANIC BODIES.

APPLICATION FILED JAN. 12, 1906. RENEWED 001. e, 1908.

Patented Mar. 2, 1909.

2 SHEETS-SHEET 1.

C. ELLIS & K. P. MOELROY.

PROCESS OF GHLORINATINQ ORGANIG BODIES.

APPLICATION IILED JAN. 12, 1906. RENEWED 001'. e, 1908.

Patented M21122, 1909.

2 SHEETS-SHEET 2.

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OARLETON ELLIS, OF WHITE PLAINS, NEW YORK, AND KARL P. MoELROY, OF WASHINGTON,

DISTRICT OF COLUMBIA, ASSIGNORS TO FIREPROOF PRODUCTS COMPANY, A CORPORA- TION OF NEW JERSEY.

PROCESS OF CHLORINA'IIIIG ORGANIC BODIES. 7

Specification of Letters Patent.

Patented March 2, 190a.

Application filed January 12, 1906, Serial No. 295,730. Renewed October 6, 1908. Serial No. $56,416.

To all whom it may concern: I

Be it known that we, OARLETON ELLIs and KARL P. MoELRoY, citizens of the United States, iesiding, respectively, in Y'Vhite Plains, county of Westchester, State of New York, and \Vashington, District of Columbia, have invented certain new and useful Improvements in Processes of Chlorinating OrganicBodies; and we hereby declare the following to be a full, clear, and exact description of the same, such as will enable others skilled in the art to which it appertains to practice and use the same.

T his invention relates to improvements in processesof chlorinating organic bodies, and consists irr-a new and useful method of treating certain, aromatic hydrocarbons and other owanic'b'odics to obtain a great variety of chlorinated products susceptible ofeconomic use; all as more fully hereinafter set forth, matters of novelty being particularly pointed out in the appended claims.

We have discovered that if certain aromatic hydrocarbons, and particularly those containing a plurality of rings, or polycyclic, are chlorinated a wide variety of useful products of varied nature maybe obtained, some being of -a desirable waxy nature, others oily, others thin liquids, etc, and we have invented a simple, cheap and easy method of performing this chlorination.

The hydrocarbons particularly adapted for treatment by our new process to produce derivatives of the character sought are those containing a plurality of rings and solid at ordinary temperatures, such as anthraccne, naphthalene, etc, their mixtures, homologues and side chain derivatives. Such waste commercial products as coal tar dead oil, containing these solid hydrocarbons in solu ,tion and sus cnsion, are also intended to be embraced within the purview of our inven' tion. These solid aromatic hydrocarbons as such have very little value in the markets at present, naphthalene being mainly used for moth balls, for disinfecting and for carbureting gas; and anthracene as a component of chea lubricating greases. Both are of course ikewise employed for making dyestuffs, but this use calls for no great amount of either; and the gross quantity so employed i robably does not exceed a few tons annually. Both are, in fact, practically waste products for which there is no market of importance, and they are, conse uently, extremely chea Naphthalene 1n a pure state can be 0 tained for less than2 cents a pound; pure anthracene would perha s be even cheaper were there an demand or it. The reason for this lack of emand commerciall y is simply that neither body has any physical property ada ting it to the common uses of lite, while on t e other hand as commonly met with, they have a nauseous odor and other unpleasant and dangerous characteristics, such as volatility, ready inflammability, etc. We have however discovered that by simply chlorinating these hydrocarbons by a simple, cheap and easy process, we can convert t 1cm into substances of great utility, nearly all of which are destitute of objectionable odor, volatility or inflammability. Such derivatives of naphthalene are particularly useful, and we shall speak hereinafter mainly of the treatment of napthalene, it bein understood that our process is ec'ually applicable to anthracene and the ot ier bodies mentioned.

Chlorin acts on naphthalene both as a substitut-ing body, replacing hydrogen with the evolution of HCl, and as a purely additive body. Derivatives formed-in either or both ways are distinguished by great stability, many withstanding very high heats, not being affected by acid, by alkali or by light or air. They are also uninflammable to an extent proportionate to the per cent. of chlorin contained, and this fact adds materially to their utility for many purposes, especially in the case of the oily and Waxy bodies. Many are true waxes, as for instance the hexachlorinated derivative. This substance contains over 60 per cent. of chlorin, is a soft, pliable wax, is eminently desirable-in physical properties for many purposes, and is practical y uninflarnmable and unaffected by ordinary heat or chemicals. Many other of the chlarinated products are equally desirable bodies, and the number of them which can be formed by our process is almost endless, it being possible by slight alterations of the conditions to form 'uite. different bodies. For instance, one ch orinated naphthalene is an oil which does not solidify at the coldest temperatures of winter though boiling at a tern erature above the melting point of tin, w ile another, produced in nearly the same manner and containing the same per centage of chlorin, is a solid at summer temperatures.

Chlorination of organic .bodies to obtain definite or uniform roducts, especially where a far-reaching ch lorination is sought, is a troublesome and uncertain operation as usually performed, and is moreover tedious and expensive. It is usually re arded as necessary to employ expensive ha ogen carriers, such as iodm, antimony chlorid, alumi-. num chlorid, etc. the bulk of which is either wasted or passes into the chlorinated body produced to contaminate it, necessitating an expensive further treatment to remove and recover these chemicals. We have however discovered that if chlorin is brought into contact with these hydrocarbons in the eculiar or nascent state in which it isevo ved by electrolysis of ordinary m'etallic chloride, and if certain precautions be taken in regard to temperature of reaction and other conditions, 1t is ossible, eas and cheap to produce from t is said by rocarbons the valuable bodies before mentioned. As to the cause of this peculiarly favorable condition of the electrolytic chlorin for producing these reactions, we are unable to speak definitely, but it is apparently due to something more than a mere condition of nascency. Perhaps the halogen atoms or ions still retain the electric charges or other properties given them in electrolysis. We content ourselves with noting the fact without endeavoring to ex lain it further.

roadly stated, our method consists in electrolyzing a suitable chlorid and leading or bringing the evolved chlorin into direct contact With the h drocarbon to be chlorinated. The chlori may be any chlorid susceptible of electrolysis, but of course in prac-' tice sodium chlorid or. potassium chlorid is enerally used. The electrolytic apparatus in which the chlorin is formed may be of any of the ordinary commercial types, its specific form being of but incidental im ortance.

The hydrocarbon to be chlorinate may be placed directly in the anode chamber, either as such or in solutionin a suitable indifferent body, such as chloroform, tetrachlorid of carbon or one of the oily chlorinated bodies formed by the present method. When placed in said chamber without solution, it is as a rule advisable to liquefy or vaporize it by heat, to accelerate the reaction and make it permeable to the chlorin, and also to facilitate feed of the raw material. As a rule however, and especially inthe case of naphthalene and anthracene, we prefer to conduct the whole chlorination with the hydrocarbon in the vaporized condition and contained in a chamber structurally separate from the chlorin evolving 'chamber, this permitting a more exact control of temperature, admixture and amount of the reacting bodies and facilitating a reaction.

contact with the mercury is made by 8.

caustic soda as, usual.

other conditions of vital im ortance in obtaining specific products. his chlorinating chamber is preferably: provided with temperature controlling means, and for many chlorinations is preferably at least partly of glass to permit illumination. Actinic light is often useful in facilitating the reaction. As a source of such light, we find well ada )ted the ordinary electric lights, and particu arly the mercury va )0! lamp. We have further discovered that the presence of an inorganic catalyzer is often of importance in Such substances as iron oxid, pumice stone, boneblack, charcoal or copper oxid are useful for this purpose. The use of electrolytic chlorin in a temperature-controlled lighted tube or chamber and in the presence of these inorganic catalyzers, is advantageous for making chlorin derivatives of many organic bodies besides the polyring hydrocarbons hereinbefore specified, as

for instance in chlorinating benzene, toluene and other benzene derivatives, in chlorinating arafhn hydrocarbons, in forming chlorin cerivatives of acids, etc.

In the accompanying illustration we show, more or less, diagrammatically, sundry forms of the wide variety of apparatus suitable for performing our process.

In this illustration, Figure 1 is a vertical section of one form of apparatus; Fig. 2 is a vertical section. of another form, and, Fig. 3 is a vertical section of a third form.

The apparatus sl'sownin Fig. 1 is a slightly modified form of an ordinary type of wet electrolytic apparatus. This apparatus, 1, comprises a truce-celled vesse a orous dialiragm 2, separating off the cl; am er containmg the anode, 3,from the com )artments containing tl-e cat's? ode, a layer 0 metallic mercurv, 4. These compartments are formed by an im ervious partition, 5, extending from ti" e top of the vessel nearly to 'tlebottom and into the mercuryjlayer. Through this partition extends avertical shaft, 6, carrying a stirrer, 7, rotating in the mercury layer. Electrical Tie functions .of these two compartments are those usual in apparatus of this character. The metallic sodium formed in the brine compartment 9 is deposited in the mercury cathode a, the amalgam. formed carried around by the stirrer into the water compartment .10 and there decomposed, forming It may be here mentioned that the formation ofi' custic soda in our process aids materially in eheapening tic cost. of our chlorinated products; The nap: thalene, etc. is fed into the anode compart' ment 12, through the feeding device 11 and tlie chlorinated products are withdrawn through 13. The specific gravity of naphth alene is but a little higher than that of" wate r While that of the chlorinated products, though varying with the specific substances,

thalene vapor, unchanged chlorin and hydroeraser is distinctly higher, so that the specific grave ity of the brine in the anode compartment can be adjusted so as to float unchanged naphthalene while allowing the chlorinated product to sink. In order to permit heating of the liquid sutficiently to keep the naphtha lene melted, the anode compartment 13 provided with a steam jacket at its base, 14, said steam jacket having the usual steam inlet, 15, and steam outlet, 16.

Fig. 2 shows a simple wet rocking electrolytic cell of the ordinary type arranged to form and deliver chlorin into a separate chamber wherein the chlorination is erformed. Apparatus 20, as a whole, is roc 'ed by cam 21 on pivot 22, running the mercury layer, 23, between compartments-24 and 25. 26 and 26 are anodes; 27, the cathode. Tubes 28 take away the chlorin, being provided with elastic parts, 29, to permit the rocking of the cell. it chamber 28 may contain hygroscopic material. Tube 28 passes through the jacket 30 to permit temperature regulation, and commumcates with passage 31. This passage, 31, is at an incline to permit heavy vapors of naphthalene or the liquid naphthalene, or, generally, both, to flow down it from melting vessel 32. A steam pipe 33, below the passage 31, permits the temperature therein to be kept at a suitable point. Volatile chlorinated products, naphchloric acic vapor pass up through tube 34 to the chamber 35, surrounded by cooling pipes 36, where condensable bodies are condensed, the chlorin and hydrochloric acid assing on ward through pipe 37 to be con ensed and separated in apparatus not here shown. The non-volatile chlorinated bodies flow oil through pipe In Fig. 3, 40 represents a furnace with grate 41, and electrolytic cell 42, provided. with an electrode 43 and liquid metal electrode 44 and tubes 45, 46 for leading off the products 1 of electrolysis, this cell being of the usual fused -salt type. The chlorin passes out through tube 46 provided with the valve 47 and enters reaction chamber 48 where it meets naphthalene vapor coming from tube:

the molecule to obviate the smell, volatility,

49, provided with valve 50, which communicates with a naphthalenevaporizing pot 51, mounted in furnace 52. Tube or chamber 48 is provided with the temperature-controlling acket 53. It is usually of glass in small sizes, and in larger is provided with windows through which shines the actinic light from lamp 5 4. Passing downward through cham ber 48, the admixed chlorin and naphthalene enter a continuing chamber 55, containing solid catalytic material, 56. Thence they chamber 57, provic ed with cooling means 58, whence the condensed chlorin derivatives are removed by the gate 59. The unchanged gaseous products pass out of chamber 57 1 through the pipe 60 into a washing chamber 61. This usually contains an oily chlorination product or other suitable body, which will remove any volatile naphthalene product. Chlorin and hydrochloric acid pass onward and outward through pipe 62 into washer 63 where the latter is abstracted by solution in j water while the former is removed by a suitable suction device 65 through tube 64. The chlorin may be utilized in any suitable way, but preferably it is absorbed by a hot partlychlorinated naphthalene which may later be completely chlorinated in the main apparatus.

In many reactions of chlorin on naphtha lene, hydrochloric acid is produced; half the chlorin going into the molecule and re lacing hydrogen, and this hydrogen forming ydrochloric acid with the other half. It is one of the economies of our process that the chlorin not going into our finished chlorinated products is nevertheless recovered in a commercially valuable form. Together with the caustic soda or potash formed in the electrolytic cell, which may of course also be recovered, it aids mater-ally in cheapening the cost of our process.

In its preferred form, our rocess consists in electrolyzing a suitable c lorid, bringing the evolved chlorin into contact with the specified hydrocarbons in a fluid form, either as liquid or vapor, regulating the tempera ture of the mixture and, usually, illuminating it with actinic rays, passing it through a catalyzer, separating the chlorination products and recovering the hydrochloric acid formed in substitution. In its specific form, as carried out in the apparatus shown in Fig.

.3, We regard it as adapted to organic chlorinations generally. The advantages of this specific form, using the hydrocarbon, etc., in the vaporous form, is that it permits the use of the solid catalyzers in a very etlicient manner, and also permits rigid control of mixing, temperatures, proportions, etc., of chlorin and hydrocarbon. But for many chlorinated products of naphthalene and anthracene, the simple treatment in the anode chamber is suilicient. It is frequently desirable to introduce merely enough chlorin into etc., of the hydrocarbon, and for this purpose the comparatively low temperature reactions in the cell are best adapted. In this form, the hydrochloric acid formed is at once electrolyzed to furnish new chlorin.

What we regard as novel and desire to secure by Letters Patent of theUnited States,

1. The process of forming useful products from the solid aromatic hydrocarbons which consists in electrolyzing a hlorid and causing the evolved chlorin to react upon such hydrocarbon.

2. The process of forming useful products from the solid aromatic hydrocarbons which from the solid aromatic hydrocarbons which consists in electrolyzing a chlorid and causing the evolved chlorin to react upon such hydrocarbon in a vaporous form.

4. The process of forming useful products from naphthalene which consists in electrolyzing a chlorid and causing the evolved chlorin to react upon naphthalene.

- 5. The process of forming useful products from naphthalene which consists in electrolyzin a ehlorid and causing the evolved chlorin to react upon naphthalene in a fluid form.

6.- The processof forming useful products from naphthalene which consists in electrolyzing a chlcrid and causing the evolved chlorin to react upon naphthalene in a vaporous form. 7. The process of'forming useful products from the solid aromatic hydrocarbons which consists in electrolyzing a chlorid, causing the evolved chlorin to react on such hydrocarbon and separately recovering the organic reaction products and hydrochloric acid.

8. The process of forming useful products from naphthalene whichcon'sists in electrolyzing a chlorid, causing the evolved chlorin to react upon naphthalene and separately recovering the organic reaction products and hydrochloric acid.

9. The rocess of chlorinating solid aromatic hyd o'carbons which consists in electrolyzing' a ehlorid, passing the evolved chlorin into a temperature-controlled chain-- her and admixing therew'iththe vapors of 40 the body to be chlorinated.

j 10. The rocess of chlorinating organic bodies whie consists in electrolyzing a chlorid, passing the evolved chlorin into a temperature-controlled chamber, admixing there with the-vapors of the organic body to be chlorinated, passing the mixture through an inorganic catalyzer and recovering. the reaction roducts.

r he rocess of chlorinat ngorganic bodies whic consists in electrolyzing'j-a' chl0 I rid, passing the evolved chlorin into ateni perature controlled chamber, therewith the vapors of the organic body to be chlorinated under the influence of actinic light, passin the mixture through an inorganic cata yzer and recovering'the reaction products. 1

12. The process of chlorinating na hthapassing the evolved chlorin into a tem erature-controlled chamber and admixing t erewith na hthalene va ors.

13. e process 0 chlorinating na hthalene which consists in electrolyzing a c lorid, passing the evolved chlorin into a tem erature-controlled chamber, admixing t lorewith vapors of naphthalene, passing the mixcovering the reaction products.

14. The process of chlorinating na hthalene which consists in electrolyzing a c lorid, passing the evolved chlorin into a temperature-controlled chamber, admixing therewith naphthalene vapors under exposure to actinic light, passing the mixture through an inorganic catalyzer, and recovering the reaction products.

I 15. The process of forming useful products from normally solid aromatic hydrocarbons which consists in reacting with electrolytically generated .chlorin upon such hydrocarbons in the fluid state and separately recovering the reaction products.

16. The process of forming useful products from naphthalene which consists'in reacting with electrolytically enerated chlorin upon the naphthalene whiTe in a fluid state and se arately recovering the reaction products. in testimonywhereof we hereunto affix our signatures, each in the presence of two witnesses.

CARLETON ELLIS. K. P. MoELROY.

Witnesses for C. Ellis:

FLETCHER P. SCOFIELD, FRED 1. SMITH.

Witnesses for K. P. McElroy:

FR D I. SMITH, PARKER H. SWEET, Jr.

admixing lene which consists in electrolyzing a c orid,

ture through an inorganic catalyzer, and re- 

